EP1047763B1 - Saure wässrige reinigungszusammensetzungen - Google Patents

Saure wässrige reinigungszusammensetzungen Download PDF

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Publication number
EP1047763B1
EP1047763B1 EP99901442A EP99901442A EP1047763B1 EP 1047763 B1 EP1047763 B1 EP 1047763B1 EP 99901442 A EP99901442 A EP 99901442A EP 99901442 A EP99901442 A EP 99901442A EP 1047763 B1 EP1047763 B1 EP 1047763B1
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Prior art keywords
composition
weight
cleaning
alkyl
compositions
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EP99901442A
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English (en)
French (fr)
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EP1047763A1 (de
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Alan Edward Sherry
Jeffrey Lawrence Flora
Jason Michael Knight
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2072—Aldehydes-ketones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • This invention relates to liquid detergent compositions for use in cleaning hard surfaces, particularly bathroom surfaces.
  • Such compositions typically contain detergent surfactants, solvents, builders, etc.
  • Known liquid detergent compositions comprise organic cleaning solvents, detergent surfactants, and optional detergent builders and/or abrasives.
  • WO-A-9 715 649 discloses an aqueous hard surface cleaning composition which comprises an acid sequestrant constituent, a mixture of hydrophobic and hydrolic solvents, and a surfactant and/or hydrotope constituent.
  • Liquid cleaning compositions have the great advantage that they can be applied to hard surfaces in neat or concentrated form so that a relatively high level of, e.g., surfactant material and/or organic solvent is delivered directly to the soil. Therefore, liquid cleaning compositions have the potential to provide superior soap scum, grease, and oily soil removal as compared to dilute wash solutions, e.g., those prepared from powdered cleaning compositions.
  • the present invention provides aqueous acidic hard surface cleaning compositions suitable for removal of soils commonly encountered in the bathroom, said compositions having specific mixtures of surfactants, solvents, and organic acids. These acidic hard surface cleaning compositions remove soap scum and hard water marks.
  • the compositions can have disinfectant properties achieved through the choice of actives, including citric acid and cationic surfactants, and can be used with or without additives such as hydrogen peroxide for additional mold/mildew prevention benefits. Further, the compositions can advantageously incorporate one or more hydrophilic polymers for improved surface wetting and filming/streaking properties.
  • the hard surface detergent cleaning compositions herein comprise:
  • compositions of the invention are especially useful for cleaning soils that are commonly encountered in the bathroom. These include dust particles, hard water stains, fatty acids, triglycerides, lipids, insoluble fatty acid soaps, and the like.
  • the detergent compositions can be used on many different surface types, such as ceramic, fiber glass, polyurethane, and plastic surfaces.
  • Alkyl benzene sulfonates are an essential component of the invention. Due to their ubiquitous nature, such surfactants provide considerable cost advantages versus other anionic surfactants. Suitable alkyl benzene sulfonates can be neutralized with any alkali metal such as lithium, sodium, potassium and the like, or can alternatively be neutralized with an ammonium or C 1 -C 9 ammonium salt derivative such as mono-ethanol amine, diethylamine and tri-isopropanol amine. They can be produced via any suitable process, leading to the formation of either "low 2-phenyl” or "high 2-phenyl” derivatives, though the "low 2-phenyl” derivatives are generally preferred.
  • Such surfactants are commercially available from several suppliers globally, including Witco Corporation (One American Lane, Greenwich, Connecticut 06831), Stepan Company (Edens & Witnetka Rd, Northfield, Illinois 60093) and BASF Aktiengesellschaft (ESA/1550, D-67056 Ludwigshafen, Germany).
  • compositions according to the present invention are prepared with relatively low levels of active.
  • compositions will comprise sufficient surfactant and solvent, as discussed hereinafter, to be effective as hard surface cleaners yet remain economical; accordingly they typically contain from 0.5% to 5% alkyl benzene sulfonate surfactant, more preferably from 1% to 4% alkyl benzene sulfonate surfactant, and even more preferably from 1.2% to 3% alkyl benzene sulfonate surfactant.
  • low levels of surfactant can also be advantageous to overall cleaning performance.
  • at levels of alkyl benzene sulfonate higher than 5% hard water mark removal is observed to deteriorate. While not wishing to be limited by theory, it is believed that high levels of surfactant compete for surface sites with the polycarboxylic acid required in the present invention, thus inhibiting the action of the organic acid.
  • the alkyl benzene sulfonates comprised in the cleaning composition according to benzene the invention have a chain length average of from 8 carbon atoms to 14 carbon atoms, more preferably from 9 carbon atoms to 13 carbon atoms, most preferably from 9 carbon atoms to 13 carbon atoms.
  • the chain length distribution can vary from 8 carbon atoms to 16 carbons. Mixtures of linear and/or branched alkyl benzene benzene sulfonates are suitable.
  • Ammonium and sodium salts of C 11 to C 12 linear alkyl benzene sulfonates are most preferred in the context of the present invention.
  • Examples of particularly preferred, commercially available sodium alkyl benzene sulfonates include Polystep A-13® available from Stepan, Calsoft L-40® slurry available from Pilot Chemical Company (11756 Burke Street, Santa Fe Springs, California). and Witconate P1059® available from Witco Corporation (Greenwich, Connecticut).
  • the desired alkyl benzene sulfonate surfactant can be produced in-situ by neutralization of the corresponding alkyl benzene sulfonic acid.
  • suitable alkyl benzene sulfonic acids include Biosoft® 100 available from Stepan Company, Calsoft LAS-99® available from Pilot Chemical, and Lutensit A-LABS® available from BASF AG in Germany.
  • compositions can also contain one or more hydrophobic cleaning solvents at effective levels, typically no less than 2%, and, at least, in increasing order of preference 2% and 3%, and no more than in increasing order of preference, 8% and 6% by weight of the composition.
  • hydrophobic cleaning solvent it is meant an agent which remove hydrophobic soils such as those commonly encountered in the bathroom.
  • the hydrophobic cleaning solvent also can participate in the building of viscosity, if needed, and in increasing the stability of the composition.
  • Such solvents typically have a terminal C 3 -C 6 hydrocarbon attached to from one to three ethylene glycol or propylene glycol moieties to provide the appropriate degree of hydrophobicity and, preferably, surface activity.
  • Examples of commercially available hydrophobic cleaning solvents based on ethylene glycol chemistry include mono-ethylene glycol n-hexyl ether (Hexyl Cellosolve® available from Union Carbide).
  • hydrophobic cleaning solvents based on propylene glycol chemistry examples include the di-, and tri-propylene glycol derivatives of propyl and butyl alcohol, which are available from Arco Chemical, 3801 West Chester Pike, Newtown Square, PA 19073) and Dow Chemical (1691 N. Sweede Road, Midland, Michigan) under the trade names Arcosolv® and Dowanol®.
  • preferred solvents are selected from the group consisting of ethylene glycol mono-hexyl ether, tri-propylene glycol butyl ether and di-propylene glycol butyl ether; the ethylene glycol mono-hexyl ether and tri-propylene glycol butyl ether are particularly effective when used in combination with di-propylene glycol butyl ether.
  • “Butyl” includes both normal butyl, isobutyl and tertiary butyl groups.
  • Di-propylene glycol butyl ether is most preferred cleaning solvent and is available under the trade names Arcosolv DPnB® and Dowanol DPnB®.
  • Di-propylene glycol t-butyl ether is commercially available from Arco Chemical under the tradename Arcosolv PTB®.
  • the amount of hydrophobic cleaning solvent can vary depending on the amount of other ingredients present in the composition, but should be present in concentrations of at least, in increasing order of preference, 2% and 3%, and less than, in increasing order of preference, 8, 6%, and 5%, by weight of the total composition.
  • the hydrophobic cleaning solvent is required to provide acceptable cleaning. It is believed that the solvent acts to remove soils that bind the other soils to the surface, or to loosen those soils so that they can be more easily reached and/or removed.
  • the detergent compositions of the present invention optionally, but preferably include an anionic cosurfactant.
  • Such surfactants typically comprise a hydrophobic chain containing from 8 carbon atoms to 18, preferably from 10 to 16, carbon atoms, and include a sulfate, sulfonate or carboxylate hydrophilic head group.
  • suitable preferred anionic surfactants include linear or branched alkyl sulfate detergent surfactant (e.g., Stepanol AM® from Stepan), alkyl ethoxy sulfates (Witconate 7093® from Witco corporation, One American Lane, Greenwich, Connecticut).
  • linear and branched C 8 -C 14 alkyl sulfate surfactants are preferred as they offer improved hard water removal benefits, and can also improved soap scum cleaning.
  • the alkyl sulfate surfactant also helps provide improved phase stability.
  • the optional anionic can be used advantageously to improve hard water performance, it is more expensive than LAS and can induce higher levels of suds.
  • the level of optional anionic surfactants in the compositions herein is from 0.25% to 4%, more preferably from 0.5% to 3.5%, most preferably from 0.75% to 3%, by weight of the composition.
  • the detergent compositions of the present invention can optionally comprise one, or more nonionic alcohols, and/or cationic surfactants.
  • the combination of the alkylaryl detergent surfactant with the alcohol and/or cationic can provide higher viscosity, as disclosed in copending provisional application Serial No. 60/066,563, filed on November 26, 1997, in the names of Alan E. Sherry, Jeffrey L. Flora, Jason M. Knight, and Zuchen Lin. Applicants claim the benefit of said application's filing date.
  • Cleaning compositions comprising both nonionic alcohol and cationic surfactant can be employed.
  • nonionic alcohol means a linear or mono-branched nonionic alcohol comprising an average of from 8 carbon atoms to 16 carbon atoms, more preferably from 9 carbon atoms to 14 carbon atoms, most preferably from 10 carbon atoms to 13 carbon atoms.
  • suitable nonionic alcohols include 2-butyl-1-octanol 2-methyl-1-undecanol and dodecanol.
  • Linear C10-13 nonionic alcohols are most preferred.
  • preferred, commercially available nonionic alcohols include Neodol 1® and Neodol 23® available from Shell Chemical (1 Shell Plaza, Houston, Texas 77252).
  • nonionic alcohols comprising less than 8 carbon atoms or longer than 16 carbon atoms are not preferred in this invention. If present, the nonionic alcohol is present in effective concentrations not exceeding 2%, more preferably in concentrations of 1.5% or less, most preferably in concentrations of 1.25% or less by weight of the composition.
  • Detergent compositions herein that do not contain a nonionic alcohol can contain one, or more, cationic surfactants.
  • cationic surfactants are those which at acidic pH behave substantially as cationic materials.
  • the cationic surfactant is to creates viscosity via ion pairing with the alkyl aryl sulfonate surfactant disclosed hereinbefore.
  • Cationic surfactants can also provide disinfectancy properties and can be selected so as to enhance such benefits.
  • Preferred cationic materials are quaternary ammonium compounds that have at least one hydrophobic chain with lengths of from 8 carbon atoms to 16 carbon atoms, more preferably from 10 carbon atoms to 16 carbon atoms, most preferably from 12 carbon atoms to 14 carbon atoms.
  • Suitable cationic surfactants include quaternary alkyl and alkyl benzyl ammonium salts (e.g., Bardac® 208M from Lonza Incorporated, 1717 Route 208, Fairlawn, New Jersey 07410) and ethoxylated quaternary ammonium salts (e.g., Ethoquad® surfactants available from Akzo Nobel Chemicals, 300 South Riverside Plaza, Chicago, Illinois).
  • cationic surfactants include ethoxylated amines (e.g., Ethomeen® surfactants available from Akzo Nobel Chemical), alkyl dimethyl betaines (e.g., Rewoteric AM DML-35® from Witco Corporation) or amido propyl betaines (e.g., Rewoteric AMB 15U® from Witco Corporation) and amine oxides (e.g., Barlox 10S® from Lonza Incorporated). Incorporation of quaternary ammonium surfactants is particularly preferred for compositions intended to deliver antibacterial, fungistatic and fungicidal properties.
  • Ethomeen® surfactants available from Akzo Nobel Chemical
  • alkyl dimethyl betaines e.g., Rewoteric AM DML-35® from Witco Corporation
  • amido propyl betaines e.g., Rewoteric AMB 15U® from Witco Corporation
  • amine oxides e.g., Bar
  • Quaternary ammonium surfactants are known in the art and include C10-16 alkyl tri-methyl ammonium, C8-14 di-alkyl dimethyl ammonium and C10-16 alkyl dimethylbenzyl ammonium derivatives and mixtures thereof. Suitable and commercially available C10-16 alkyl tri-methyl ammonium and C8-C14 di-alkyl dimethyl ammonium quaternaries are available from Witco corporation under the tradename Adogen®; suitable C10-16 alkyl dimethylbenzyl ammonium surfactants may be purchased from Lonza incorporated under the tradename Bardac®.
  • the counter-ion of the quaternary ammonium surfactants may be any of those known in the art such as bromide, chloride or methyl sulfate.
  • the preferred counter-ion is methyl sulfate.
  • the level of cationic surfactant in the compositions of the present invention is preferably no greater than 2%, more preferably no greater than 1.5%, most preferably no greater than 1.25% by weight of the composition.
  • Cationic surfactants can be used alone or in combination with nonionic alcohols for viscosity.
  • the level of cationic surfactant plus nonionic alcohol comprises at least 0.1%, more preferably at least 0.3%, most preferably at least 0.5%, and still more preferably from 0.5% to 2.0%, by weight of the composition.
  • the compositions are acidic with a pH of from 2 to about 4, more preferably 3. Acidity is accomplished , at least in part, through the use of one or more organic acids that having a pKa of less than 5, preferably less than 4. Such organic acids also can assist in phase formation for thickening, if needed, as well as provide hard water stain removal properties. It is found that organic acids are very efficient in promoting good hard water removal properties within the framework of the compositions of the present invention. Lower pH and use of one or more suitable acids is also found to be advantageous for disinfectancy benefits. Examples of suitable organic acids include citric acid, tartaric acid, succinic acid, glutaric acid, adipic acid, and mixtures thereof. Such acids are readily available in the trade.
  • Examples of more preferred acids include citric acid (available from Aldrich Corporation, 1001 West Saint Paul Avenue, Milwaukee, Wisconsin) and a mixture of succinic, glutaric and adipic acids available from DuPont (Wilmington, Delaware) sold as "refined AGS di-basic acids". Citric acid is most preferred.
  • the amount of organic acid in the compositions herein can be from 1% to 10%, more preferably from 2% to 8%, most preferably from 3% to 6% by weight of the composition.
  • compositions of the invention can contain peroxide such as hydrogen peroxide, or a source of hydrogen peroxide, for further disinfectancy, fungistatic and fungicidal benefits.
  • Peroxide is believed to enhance the longevity of the benefit because of its well known residuality and slow decomposition to produce radical species.
  • the components comprised in the cleaning composition according to the present composition are substantially compatible with the use of peroxides.
  • Preferred peroxides include benzoyl peroxide and hydrogen peroxide. These can optionally be present in the compositions herein in levels of from 0.05% to 5%, more preferably from 0.1% to 3%, most preferably from 0.2% to 1.5%.
  • a stabilizing system consists of radical scavengers and/or metal chelants present at levels of from 0.01% to 0.5%, more preferably from 0.01% to 0.25%, most preferably from 0.01% to 0.10%, by weight of the composition.
  • radical scavengers include anti-oxidants such as propyl gallate, butylated hydroxy toluene (BHT), butylated hydroxy anisole (BHA).
  • suitable metal chelants include diethylene triamine penta-acetate, diethylene triamine pentamethylene phosphonate, hydroxyethyl diphosphonate.
  • Optional hydrophilic polymer :
  • compositions of the present invention can advantageously incorporate low levels of hydrophilic polymer.
  • hydrophilic polymer have been found to enhance water sheeting on surfaces and improve filming streaking as disclosed in copending provisional application Serial No. 60/061,296, filed on October 7, 1997, in the names of Nicola John Policicchio and Alan Edward Sherry. While not wishing to be limited by theory it is believed that such polymers hydrophilically modify ceramic surface thereby reducing water surface tension and inducing improved water sheeting on said surfaces. This sheeting effect allows for channeling of dissolved soils down shower walls in bathrooms, leading to lower residual soil levels.
  • Hydrophilic polymers have also been shown to mitigate the surface spotting caused by surfactants, especially for compositions that additionally include quaternary ammonium surfactant.
  • Preferred hydrophilic polymers to be used in conjunction with compositions of the present invention include xanthan gum, polystyrene sulfonate, polyvinyl pyrrolidone, polyvinyl pyrrolidone/acrylate copolymer, polyvinyl pyridine and polyvinyl pyridine n-oxide.
  • the most preferred polymers are polyvinyl pyridine and polyvinyl pyridine n-oxide.
  • the preferred polymers if present, have an average molecular weight of from 10,000 to 5,000,000, more preferably from 20,000 to 1,000,000, most preferably from 30,000 to 500,000.
  • the level of polymer desired to achieve the desired benefits is from 0.001% to 0.10%, more preferably from 0.005% to 0.075%, most preferably from 0.01% to 0.05%.
  • the specific level of polymer depends on the formulators objective. Thus, while improved sheeting results from increased level of polymer, it is also found that hard water removal performance deteriorates.
  • compositions of the present invention preferably comprise other additional anionic surfactants such as paraffin sulfonates (Hostapur SAS® from Hoechst, Aktiengesellschaft, D-6230 Frankfurt, Germany) and alkyl ethoxy carboxylates detergent surfactant (Neodex® from Shell Chemical Corporation).
  • paraffin sulfonates Hostapur SAS® from Hoechst, Aktiengesellschaft, D-6230 Frankfurt, Germany
  • alkyl ethoxy carboxylates detergent surfactant Naeodex® from Shell Chemical Corporation
  • Nonionic detergent surfactants can also be present.
  • Suitable nonionic detergent surfactants for use herein are alkoxylated alcohols generally comprising from 6 to 16 carbon atoms in the hydrophobic alkyl chain of the alcohol.
  • Typical alkoxylation groups are ethoxy and/or propoxy groups.
  • Such compounds are commercially available under the series Neodol® from Shell, or Lutensol® from BASF AG with a wide variety of chain length and alkoxylation degrees.
  • nonionic detergent surfactants for use herein are according to the formula R(X) n H, were R is an alkyl chain having from 6 to 16 carbon atoms, preferably from 6 to 10, X is an alkoxy group, preferably ethoxy, or a mixture of ethoxy and propoxy groups, n is an integer of from 4 to 30 preferably 5 to 8.
  • Other non-ionic surfactants that can be used include those derived from natural sources such as sugars and include alkyl polyglucosides (e.g., Simusol® surfactants from Seppic Corporation, 75 Quai d'Orsay, 75321 Paris, Cedex 7, France) and N-alkyl glucose amide surfactants. If present, the concentration of nonionic surfactant is from 0.1% to 3%, more preferably from 0.1% to 2%, by weight of the composition.
  • compositions of the present invention can also include zwitterionic surfactants such as sulfobetaines and hydroxy sulfobetaines in effective concentrations preferably not exceeding 2% by weight of the composition.
  • compositions are aqueous, comprising at least 60% aqueous solvent by weight of the composition, more preferably from 60% to 90% by weight of the composition.
  • the aqueous compositions are in micellar form, and do not incorporate substantial levels of water insoluble components that induce significant micellar swelling; the compositions are also adjusted to a final pH of from 2 to 4, preferably 3.
  • the aqueous solvent system can also comprise low molecular weight highly water soluble solvents typically found in detergent compositions, e.g., ethanol and isopropanol.
  • compositions of the present invention can also include other solvents, and in particular paraffins and isoparaffins, which have been found to substantially reduce the suds created by the composition.
  • Optional components such as perfumes and other conventional adjuvants can also be present.
  • perfume An optional, but highly preferred ingredient, is a perfume, usually a mixture of perfume ingredients.
  • perfume ingredients which are typically hydrophobic materials, have been found to provide a contribution to building viscosity, perhaps through supporting the phase structure of the product, as well as improving the overall stability of the product.
  • perfume includes constituents of a perfume which are added primarily for their olfactory contribution.
  • Most hard surface cleaner products contain some perfume to provide an olfactory aesthetic benefit and to cover any "chemical" odor that the product may have.
  • the main function of a small fraction of the highly volatile, low boiling (having low boiling points), perfume components in these perfumes is to improve the fragrance odor of the product itself, rather than impacting on the subsequent odor of the surface being cleaned.
  • some of the less volatile, high boiling perfume ingredients can provide a fresh and clean impression to the surfaces, and it is sometimes desirable that these ingredients be deposited and present on the dry surface.
  • the perfumes are preferably those that are more water-soluble and/or volatile to minimize spotting and filming.
  • the perfumes useful herein are described in more detail in U.S. Patent 5,108,660, Michael, issued April 28, 1992, at col. 8 lines 48 to 68, and col. 9 lines 1 to 68, and col. 10 lines 1 to 24, said patent, and especially said specific portion.
  • Perfume components can be natural products such as essential oils, absolutes, resinoids, resins, concretes, etc., and/or synthetic perfume components such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, acetals, ketals, nitriles, etc., including saturated and unsaturated compounds, aliphatic, carbocyclic and heterocyclic compounds.
  • perfume components are: geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalool, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, terpineol, terpinyl acetate, acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, styrallyl acetate, amyl salicylate, dimenthylbenzylcarbinol, trichloromethylphenycarbinyl acetate, p-tert.butylcyclohexyl acetate, isononyl acetate, alpha-n-amylcinammic aldehyde, alpha-hexylcinammic aldehyl,
  • compositions herein typically comprise from 0.1% to 2% by weight of the total composition of a perfume ingredient, or mixtures thereof, preferably from 0.1% to 1.0%.
  • the perfumes must be chosen so as to be compatible with the oxidant.
  • the perfume ingredients are hydrophobic and highly volatile, e.g., ingredients having a boiling point of less than 260°C, preferably less than 255°C; and more preferably less than 250°C, and a ClogP of at least 3, preferably more than 3.1, and even more preferably more than 3.2.
  • the logP of many ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP” program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database.
  • the "calculated logP” (ClogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990).
  • the fragment approach is based on the chemical structure of each ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding.
  • the ClogP values which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of the principal solvent ingredients which are useful in the present invention.
  • Other methods that can be used to compute ClogP include, e.g., Crippen's fragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21 (1987); Viswanadhan's fragmentation method as disclose in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J. Med. Chem. - Chim. Theor., 19, 71 (1984).
  • compositions herein can comprise a variety of other optional ingredients, including further actives and detergent builder, as well as mere aesthetical ingredients.
  • further actives and detergent builder as well as mere aesthetical ingredients.
  • rheology of the compositions herein would be suitable for suspending particles in the composition, e.g., particles of abrasives.
  • Detergent builders that are efficient for hard surface cleaners and have reduced filming/streaking characteristics at the critical levels are another optional ingredient.
  • Preferred detergent builders are the carboxylic acid detergent builders described hereinbefore as part of the polycarboxylic acid disclosure, including citric and tartaric acids. Tartaric acid improves cleaning and can minimize the problem of filming/streaking that usually occurs when detergent builders are added to hard surface cleaners.
  • the detergent builder is present at levels that provide detergent building, and, those that are not part of the acid pH adjustment described hereinbefore, are typically present at a level of from 0.1% to 0.3%. more preferably from 0.2% to 2%, and most preferably from 0.5 to 1%.
  • compositions herein can also contain other various adjuncts which are known to the art for detergent compositions. Preferably they are not used at levels that cause unacceptable filming/streaking.
  • Non-limiting examples of other adjuncts are: enzymes such as proteases; hydrotropes such as sodium toluene sulfonate, sodium cumene sulfonate and potassium xylene sulfonate; thickeners at a level of from 0.01% to 0.5%, preferably from 0.05% to 0.4%; and aesthetic-enhancing ingredients such as colorants, providing they do not adversely impact on filming/streaking.
  • enzymes such as proteases
  • hydrotropes such as sodium toluene sulfonate, sodium cumene sulfonate and potassium xylene sulfonate
  • thickeners at a level of from 0.01% to 0.5%, preferably from 0.05% to 0.4%
  • aesthetic-enhancing ingredients such as colorants, providing they do not adversely impact on filming/streaking.
  • Antibacterial agents in addition to the cationic ones described hereinbefore, can be present, but preferably only at levels below 0.5%, preferably below 0.4%, to avoid filming/streaking problems. More hydrophobic antibacterial/germicidal agents, like orthobenzyl-para-chlorophenol, are avoided. If present, such materials should be kept at levels below 0.1%.
  • composition making:
  • compositions herein can be made by mixing together all ingredients.
  • a preferred order of addition is to first incorporate water, alkyl aryl sulfonate surfactant and organic acid, followed the hydrophobic cleaning solvent. Once the solvent is added, pH is adjusted to optimum as desired by the formulator.
  • Optional cationic surfactant, peroxide, polymer, perfume and dye can then be added.
  • Soap Scum Cleaning Standard soiled plates that are used to provide a reproducible, standard soiled surface are treated with each product and the surface is then wiped with a sponge using a Gardner Straight line Washability Machine. The number of strokes required for complete cleaning is measured and recorded.
  • the soap scum cleaning index is calculated using the following equation: (# strokes for control product/# strokes for experimental product) * 100, where the control product is Dow Bath Room® aerosol and the experimental prototypes are compositions 1 - 8 disclosed herein. Indices greater than 100 are suggestive of products with superior soap scum removal properties.
  • Hard Water Cleaning Four marble chips for each product tested of approximate dimensions 3 ⁇ 4" x 3 ⁇ 4" x 1 ⁇ 4" are weighed to four decimal places using an analytical balance. The chips are then placed in 100 ml beakers containing 20 grams of product for a total of 10 minutes. The marble chips are then removed, rinsed and allowed to dry. They are then re-weighed and the weight lost is computed. Using averages of four trials for each product, the hard water removal index is computed as follows: (average weight loss of the marble chips immersed in the control product/average weight loss of the marble chips immersed in the experimental compositions) * 100.
  • Soap scum removal and hard water removal test comparisons are made versus a commercially available product Dow Bath Room® aerosol.
  • compositions are made by mixing the listed ingredients in the listed proportions in the listed order of addition.

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Claims (12)

  1. Saure Reinigungszusammensetzung für harte Oberflächen, die Folgendes umfasst:
    a) von 0,5 Gew.- % bis 5 Gew.- % der Zusammensetzung Alkylbenzolsulfonat-Reinigungstensid;
    b) von 1 Gew.- % bis 8 Gew.- % der Zusammensetzung hydrophobes Reinigungslösungsmittel, ausgewählt aus der Gruppe, bestehend aus: Dipropylenglycolmonobutylether; Tripropylenglycolmonobutylether; Ethylenglycolmonohexylether und Mischungen davon;
    c) von 2 Gew.- % bis 8 Gew.- % der Zusammensetzung wasserlösliche Polycarbonsäure;
    d) zu übrigen Teilen ein wässriges Lösungsmittelsystem, und
    worin die Reinigungszusammensetzungen in mizellarer Phase mit einem pH der Zusammensetzungen von 2 bis 4 sind.
  2. Zusammensetzung nach Anspruch 1, die Folgendes umfasst:
    a) von 1 Gew.- % bis 4 Gew.- % der Zusammensetzung Alkylbenzolsulfonat-Reinigungstensid;
    b) von 2 Gew.- % bis 6 Gew.- % der Zusammensetzung ein oder mehrere hydrophobe Reinigungslösungsmittel;
    c) von 2 Gew.- % bis 6 Gew.- % der Zusammensetzung Citronensäure;
    d) von 60 Gew.- % bis 90 Gew.- % der Zusammensetzung das wässrige Lösungsmittelsystem, und
    worin die Reinigungszusammensetzung einen pH von 3 aufweist.
  3. Zusammensetzung nach Anspruch 1, die Folgendes umfasst:
    a) von 1,2 Gew.- % bis 4,5 Gew.- % der Zusammensetzung Alkylbenzolsulfonat-Reinigungstensid, worin die Alkylgruppe von 8 bis 14 Kohlenstoffatome enthält;
    b) von 3 Gew.- % bis 6 Gew.- % der Zusammensetzung ein oder mehrere hydrophobe Reinigungslösungsmittel;
    c) von 3 Gew.- % bis 5 Gew.- % der Zusammensetzung Citronensäure;
    d) von 60 Gew.- % bis 90 Gew.- % der Zusammensetzung das wässrige Lösungsmittelsystem.
  4. Zusammensetzung nach Anspruch 1-3, die zusätzlich Folgendes umfasst: (e) von 0,25 Gew.- % bis 4 Gew.- % der Zusammensetzung ein anionisches Cotensid, ausgewählt aus der Gruppe, bestehend aus: linearen oder verzweigten C8-C18-Alkylsulfaten; C8-C18-Alkylethoxysulfaten; und Mischungen davon; und/oder (f) eine wirksame Konzentration, die 2 Gew.- % der Zusammensetzung nicht überschreitet, an nichtionischem Alkohol und/oder kationischem Tensid; und/oder (g) eine wirksame Menge bis zu 5 Gew.- % der Zusammensetzung an Wasserstoffperoxid; und/oder (h) eine wirksame Menge bis zu 0,1 Gew.- % der Zusammensetzung an einem hydrophilen Polymer.
  5. Zusammensetzung nach Anspruch 4, worin der nichtionische Alkohol linear oder einfach verzweigter Alkohol mit 8 bis 16 Kohlenstoffatomen ist; und/oder worin das kationische Tensid eine hydrophobe Kette mit 8 bis 16 Kohlenstoffatomen enthält; und/oder das hydrophile Polymer ausgewählt ist aus der Gruppe, bestehend aus: Xanthangummi; Polystyrolsulfonat; Polyvinylpyrrolidon; Polyvinylpyrrolidon/Acrylat-Copolymer; Polyvinylpyridin; Polyvinylpyridin-n-oxid; und Mischungen davon.
  6. Zusammensetzung nach Anspruch 4, worin das kationische Tensid ausgewählt ist aus der Gruppe, bestehend aus: C8-C18-Trialkylammoniumchlorid, C8-12-Dialkyldimethylammoniumchlorid, C8-C18-Alkylbenzyldimethylammoniumchlorid und C8-C18-Alkylpyridiniumdimethylammoniumchlorid.
  7. Zusammensetzung nach Anspruch 4-6, die von 0,001 Gew.- % bis 0,1 Gew.- % der Zusammensetzung das hydrophile Polymer umfasst.
  8. Zusammensetzung nach Anspruch 4-7, die von 0,05 Gew.- % bis 5 Gew.- % der Zusammensetzung das Wasserstoffperoxid umfasst.
  9. Zusammensetzung nach Anspruch 1-8, worin das hydrophobe Reinigungslösungsmittel Dipropylenglycol-n-butylether ist und/oder worin die Zusammensetzung Citronensäure als pH-Einsteller enthält und einen pH von 3 oder weniger aufweist.
  10. Zusammensetzung nach Anspruch 1-9, worin die Polycarbonsäure ausgewählt ist aus der Gruppe, bestehend aus: Citronensäure und Mischungen von Bernstein-, Adipin- und Glutarsäure.
  11. Verfahren zum Reinigung einer Oberfläche, umfassend das Auftragen einer wirksamen Menge der Zusammensetzung nach einem der Ansprüche 1-10 auf die Oberfläche und Abspülen der Oberfläche.
  12. Verfahren nach Anspruch 11, worin die Oberfläche mit Schimmel verschmutzt ist und die Zusammensetzung eine wirksame Menge an dem Wasserstoffperoxid, dem kationischen Tensid und/oder dem hydrophilen Polymer enthält.
EP99901442A 1998-01-12 1999-01-12 Saure wässrige reinigungszusammensetzungen Expired - Lifetime EP1047763B1 (de)

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US7118598P 1998-01-12 1998-01-12
US71185P 1998-01-12
PCT/US1999/000644 WO1999035227A1 (en) 1998-01-12 1999-01-12 Acidic aqueous cleaning compositions

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EP1047763B1 true EP1047763B1 (de) 2005-12-07

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Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2195306T3 (es) * 1998-11-11 2003-12-01 Procter & Gamble Composiciones de blanqueo.
DE60124906T2 (de) * 2000-06-05 2007-05-24 S.C. Johnson & Son, Inc., Racine Biozide reinigungsmittel
GB2398571A (en) * 2003-02-22 2004-08-25 Reckitt Benckiser Inc Acidic hard surface cleaning and/or disinfecting composition
US7119055B2 (en) 2001-08-31 2006-10-10 Reckitt Benckiser Inc. Hard surface cleaners comprising a thickening gum mixture
US7256167B2 (en) 2001-08-31 2007-08-14 Reckitt Benckiser Inc. Hard surface cleaner comprising suspended particles and oxidizing agent
GB2379223A (en) * 2001-08-31 2003-03-05 Reckitt Benckiser Inc Cleaning composition comprising citric acid
US6444636B1 (en) * 2001-12-10 2002-09-03 Colgate-Palmolive Company Liquid dish cleaning compositions containing hydrogen peroxide
AR043906A1 (es) 2003-02-22 2005-08-17 Reckitt Benckiser Inc Composiciones limpiadoras para superficies duras
GB2398792A (en) 2003-02-22 2004-09-01 Reckitt Benckiser Inc Acidic hard surface cleaning and/or disinfecting composition
US11033023B2 (en) 2014-11-26 2021-06-15 Microban Products Company Surface disinfectant with residual biocidal property
US10834922B2 (en) 2014-11-26 2020-11-17 Microban Products Company Surface disinfectant with residual biocidal property
US10925281B2 (en) 2014-11-26 2021-02-23 Microban Products Company Surface disinfectant with residual biocidal property
US10842147B2 (en) 2014-11-26 2020-11-24 Microban Products Company Surface disinfectant with residual biocidal property
EP3118294B1 (de) 2015-07-13 2018-10-17 The Procter and Gamble Company Reinigungsprodukt
EP3118295B1 (de) * 2015-07-13 2018-10-17 The Procter and Gamble Company Verwendung von glykoletherlösungsmitteln in flüssigen reinigungsmittelzusammensetzungen
EP3118299B1 (de) 2015-07-13 2018-10-17 The Procter and Gamble Company Reinigungsprodukt
EP3118301B1 (de) 2015-07-13 2018-11-21 The Procter and Gamble Company Reinigungsprodukt
EP3118293B1 (de) 2015-07-13 2020-09-09 The Procter and Gamble Company Reinigungsprodukt
WO2017091250A1 (en) * 2015-11-23 2017-06-01 Microban Products Company Surface disinfectant with residual biocidal property
EP3418363A1 (de) * 2017-06-21 2018-12-26 The Procter & Gamble Company Polymerhaltige antimikrobielle reinigungszusammensetzungen für harte oberflächen
EP3418368A1 (de) 2017-06-21 2018-12-26 The Procter & Gamble Company Lösungsmittel mit zusammensetzung zur reinigung harter oberflächen
EP3417709A1 (de) 2017-06-21 2018-12-26 The Procter & Gamble Company Lösungsmittel mit antimikrobiellen reinigungszusammensetzungen für harte oberflächen

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2143108A1 (en) * 1992-08-25 1994-03-03 Terry Instone Liquid cleaning compositions comprising primary alkyl sulphate and non-ionic surfactants
NZ264113A (en) * 1993-08-04 1996-06-25 Colgate Palmolive Co Liquid crystal or microemulsion liquid cleaners containing esterified polyethoxyether nonionic surfactant, anionic surfactant, cosurfactant, optionally a fatty acid, and water-insoluble hydrocarbon or perfume
US5716925A (en) * 1993-08-04 1998-02-10 Colgate Palmolive Co. Microemulsion all purpose liquid cleaning compositions comprising partially esterified, fully esterified and non-esterified polyhydric alcohol and grease release agent
WO1995014765A1 (en) * 1993-11-22 1995-06-01 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
US6221823B1 (en) * 1995-10-25 2001-04-24 Reckitt Benckiser Inc. Germicidal, acidic hard surface cleaning compositions
US5834413A (en) * 1997-09-26 1998-11-10 Colgate-Palmolive Co. Liquid cleaning compositions

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WO1999035227A1 (en) 1999-07-15
ATE312159T1 (de) 2005-12-15
ES2253873T3 (es) 2006-06-01
DE69928769D1 (de) 2006-01-12
EP1047763A1 (de) 2000-11-02

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